Process for control of algae growth using compositions containing diamines and/or derivatives thereof



United States Patent 01 fice 3,466,162 Patented Sept. 9, 1969 3,466,162PROCESS FOR CONTROL OF ALGAE GROWTH USING COMPOSITIONS CONTAINING DIA-MINES AND/ OR DERIVATIVES THEREOF Urs Gloor, Riehen, and Klaus Bohnen,Dielsdorf, Switzerland, assignors to Hotlmann-La Roche Inc., Nutley,N.J., a corporation of New Jersey No Drawing. Filed Feb. 7, 1967, Ser.No. 614,403 Claims priority, application Switzerland, Feb. 25, 1966,2,789/ 66 Int. Cl. A01n 9/20 US. Cl. 71--67 10 Claims ABSTRACT OF THEDISCLOSURE Diamines, and acid addition salts thereof, or quaternaryproducts produced therefrom; compositions containing same; and the useof such compounds and compositions for the control of algae.

BRIEF SUMMARY OF THE INVENTION The invention is concerned with compoundswhich have been found to be highly effective in controlling the growthof algae and with the use of such compounds. The compounds which areemployed in the practice of the invention have the formula in which thesymbol R represents an aliphatic hydrocarbon residue or acycloaliphatic-aliphatic hydrocarbon residue containing from 10 to 15carbon atoms; the symbol R represents hydrogen or a lower alkyl radical;the symbols R represents hydrogen or a lower alkyl radical; the symbol Rrepresents an aliphatic hydrocarbon residue or acycloaliphatic-aliphatic hydrocarbon residue containing from 10 to 15carbon atoms; the symbol R represents a straight or branched chainalkylene residue having from 2 to carbon atoms; with the proviso thatthe residues represented by the symbols R and R taken with the alkyleneresidue represented by the symbol R provide a total of at least 27carbon atoms.

Acid addition salts of the Formula I compounds, as well as quaternaryproducts produced therefrom, are also suitable for use in the practiceof this invention.

DETAILED DESCRIPTION The present invention provides a means foreffectively controlling the growth of algae. The compounds which areused in the practice of the invention have been found to possess a highdegree of activity against algae growth, and in use, their effectivenessis long-lasting.

In carrying out this invention, there is employed, as the algae growthcontrolling agent, at least one diamine having the formula 2 Rs 1 inwhich the symbol R represents an aliphatic hydrocarbon residue or acycloaliphtic-aliphatic hydrocarbon residue containing from 10 to carbonatoms; the symbol R represents hydrogen or lower alkyl radical; thesymbol R represents hydrogen or a lower alkyl radical; the symbol Rrepresents an aliphatic hydrocarbon residue or acycloaliphatic-aliphatic hydrocarbon residue containing from 10 to 15carbon atoms; the symbol R represents a straight or branched chainalkylene residue having from 2 to 10 carbon atoms; with the proviso thatthe residues represented by the symbols R and R taken with the alkyleneresidue represented by the symbol R provide a total of at least 27carbon atoms, or an acid addition salt of, or a quaternary productproduced from, a Formula I compound. Where, in subsequent portions ofthis specification reference is made to the compounds of Formula I, suchreference should be construed as including the diamine bases as well asacid addition salts and quaternary compounds produced therefrom.

Compounds of Formula I Whose properties are such as to make themparticularly interesting in the practice of this invention are those inwhich the substituents represented by the symbol R, and R are the sameand in which the substituents represented by the symbols R and R are thesame.

Preferred classes of compounds which fall within the scope of Formula Iare those in which the symbol R and R each represent a1,5,9-dimethyl-decyl residue, or the corresponding residue unsaturatedin the 2,3-, 4,5- and/or 8,9-position; or in which the symbols R and Reach represent a 1-methyl-3-(2,6,G-trimethylcyclohexyl)- propyl radical;or in which the symbols R and R each represent a 1methyl-3-[2,6,6-trimethylcyclohexen-(1)- yl]-propyl residue. Suchcompounds, preferably have, as

the R and R substituents, a hydrogen atom or an alkyl radical havingfrom 1 to 3 carbon atoms, especially a methyl radical. Moreover, in thecase of such compounds, where R represents a straight chain alkyleneresidue, such residue contains preferably from about 4 to 6 carbonatoms, especially, 6 carbon atom whereas, where R represents a branchedchain residue such residue contains, preferably, from about 7 to 10carbon atoms, especially 9 carbon atoms.

Thus, for example, the present invention embraces the use of diamineshaving the formula in which the symbol R and R represent a hydrogen atomor a methyl group; and R represents a polymethylene chain, which may bemethyl-substituted, having from 2 to 10, and preferably from 6 to 9,carbon atoms, and wherein double bonds indicated by the broken line canbe hydrogenated.

Acid addition salts of, and quaternary products derived from, theFormula 1(a) compounds are also suitable for use. Representative of apreferred class of compounds, embraced by Formula 1(a) are those inwhich the symbol R represents hexamethylene or a trimethyl hexamethylenegroup, such as, the 2,2-dimethyl-4-methylhexamethylene and the2-methyl-4,4-dimethyl-hexamethylene radicals. Specific examples ofcertain Formula 1(a) compounds are as follows:

N,N'-bis( 1,5,9-trimethyldecyl) -1 ,Z-ethyIenediamine N,N-bis-(1,5,9-trimethyldecyl) -N,N-dimethyl-1,2-

ethylenediamine N,N'-bis-( 1,5 9-trimethyldecyl) -N,N-dimethyl- 1,2-

ethylenediamine bis- (methobromide) N,N-bis-(1,5,9-trimethyldecyl)-1,6hexanediamineN,N'-bis-(1,5,9-trimethyldecyl)-N,N-dimethyl-1,6-

hexanediamine N,N'-bis-( 1,5,9-trimethyldecyl N,N-dimethyl- 1 ,6-

hexanediamine bismethobromide)N,N-bis-[1,5,9-trimethyldecatrien-(2,4,8)-yl]-1,6-

hexanediamine N,N'-bis-[ 1,5,9-trimethyldecaen- (4) -yl]1,6-hexanediamine N,N'-bis-( 1,5,9-trimethyldecyl 2,2-dimethyl-4-methyl-1,6-hexanediamine 3 N,N'-bis-( 1,5,9-trimethyldecyl-2-methyl-4,4-dimethyl- 1,6-hexanediamine.

In one of the preferred embodiments of the invention, a mixture ofN,N'-bis-(1,5,9-trimethyldecyl) 2,2-dimethyl-4-methyl-1,6-hexanediamineand N,N' bis-(1,5,9-trimethyldecyl) Z-methyl 4,4-dimethyl1,6-hexanediamine is used.

Additionally, there can be used in the practice of this inventiondiamines having the formula in which the symbols R R and R have the samemeaning as in Formula I(a).

Acid addition salts of, and quaternary products derived from, theFormula I(b) compounds are also suitable for use in the practice of thisinvention. As specific examples of compounds encompassed by FormulaI(b), the following can be mentioned:

N,N'-bis-{1-methyl-3-[2,6,6-trimethylcyclohexen-( lyl]-propyl}-N,N'-dimethyl-1,5-pentanediamine bis-methobromideN,N-bis(1-methyl-3-[2,6,6-trimethylcyclohexyl]-propyl)-N,N-dimethyl-1,4-butanediaminebis-(methobromide) N,N'-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]-propyl)-N,N'-dimethyl-1,4-butanediamine dihydrochlorideN,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexen-( lyl]-propyl)-N,N-dimethyl-1,6-hexanediamine bis- (methobromide)N,N'-bis-( l-methyl-3- 2,6,6-trimethylcyclohexyl]-prpyl)-N,N-dimethyl-1,5-pentanediamine bis- (methobromide)N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]- pro pyl) -N,N-dimethyl-1,6-hexanediamine bis- (methobromide)N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]-propyl)-N,N'-dimethyl-1,Z-ethanediamine bis-(methobromide) N,N-bis-(1-methyl-3- [2,6,6-trimethylcyclohexyl propyl) -1,2-ethanediamineN,N'-bis-(1-methyl-3 2,6,6-trimethylcyclohexyl]propyl)-N,N'-dimethyl-1,2-ethanediamine N,N-bis-( 1-methyl-3-[2,6,6-trimethylcyclohexyl propyl) -1,6-hexanediamine N,N-bis-(1-methyl-3- [2,6,6-trimethylcyclohexyl propyl -N,N'-dimethyll,6-hexanediamine N,N-bis-( 1-methyl-3- [2,6,6-trimethylcyclohexyl]propyl) -2,2-dimethyl-4-methyl-1,6-hexanediamine N,N-bis-( 1-methyl-3[2,6,G-trimethylcyclohexyl propyl)-2-methy1-4,4-dimethyl-1,6-hexanediamine.

In one of its preferred embodiments, the invention involves the use of amixture of N,N'-bis-(l-methyl-3- [2,6,6-trimethylcyclohexyl] propyl) 2,dimethyl-4- methyl-1,6-hexanediamine and N,N'-bis (l-methyl)-3[2,6,6-trimethylcyclohexyl] propyl) 2-methyl4,4-dimethyl-1,6-hexanediamine.

As indicated heretofore, the present invention contemplates the use ofdiamine bases of Formulas I, 1(a) and I(b) as well as acid additionsalts thereof and quaternary products derived therefrom. Suitable foruse are salts of the compounds of Formulas I, 1(a) and I(b) with organicacids, such as, acetic acid; benzoic acid; citric acid; malic acid;maleic acid; salicylic acid; tartaric acid; etc. or with mineral acids,such as, the hydrohalic acids, for example, hydrochloric acid; nitricacid; phosphoric acid; sulfuric acid; etc. Additionally, salts of thecompounds with methane sulfonic acid can be used. Furthermore, and aspreviously indicated, quaternary compounds produced from the compoundsof Formulas I, 1(a) and I(b) can be employed. These quaternary compoundsare produced, for example, by treating the base with an alkyl halide,such as, methyl bromide, or with an alkyl sulfonate, such as, dimethylsulfate.

As previously stated, the compounds of Formulas I, and, in certainpreferred embodiments of the invention, the compounds of Formulas 1(a)and I(b), are used to prevent or at least retard the growth of algae. Athigh concentrations, for example, at a level of from about 0.1 to about10 parts per million parts of the medium to be treated, the compoundsdescribed herein act to inhibit algae growth. At lower concentrations,the compounds will retard the growth of algae. The quantity of activeingredient which, in any given case, is added to the medium to betreated will determine, to a great extent, the frequency with which thetreatment is repeated. It has been found that inhibition of algaegrowth, which extends, without further treatment, over a period ofseveral weeks, is achieved when the medium is treated with from about 1to about 6 parts per million, preferably, from about 2 to about 5 partsper million, of the active ingredient. Where a lower concentration ofactive ingredient is used, it is advisable to repeat the treatment atregular intervals to compensate for the gradual inactivation of theactive ingredient.

Compounds embraced by Formulas I, 1(a) and I(b) are known. Processes fortheir production are described, for example, in the Journal of MedicinalChemistry 6, 780 (1963) and US. Patents 3,064,039 and 3,064,052. Ingeneral, however, the compounds are produced by the reductivecondensation of a diamine having the formula H N-R NH in which thesymbol R has the same meaning as in Formula I, with a suitable carbonylcompound.

The manner in which the compounds of Formulas I, 1(a) and I( b) are usedin the practice of this invention to prevent and/or inhibit the growthof algae will be readily apparent to persons skilled in the art. Forexample, the compounds can be formulated as solutions or emulsions andused as such. Alternatively, the compounds can be formulated asemulsifiable concentrates, such concentrates being converted intoemulsions prior to use. Additionally, however, the bases of Formulas I,1(a) and I(b), after having been converted into water-soluble acidaddition salts, for example, into an acetate salt, a hydrochloride saltor a sulfate salt, can be incorporated into a permeable vessel, forexample, a cloth bag. Such bag can be aflixed to a water hose in such amanner that the water leaving the hose flows through the bag into thetank or pool which is to be protected against algae growth. Byproceeding in this manner, the water-soluble salts become dissolved inthe water and are distributed throughout the tank or pool by the flow ofthe water therein. Where it is desired to prevent or inhibit the growthof algae in a swimming pool which is equipped with a rotary filterinstallation, the compound of Formulas I, I(a) or I(b), or a mixturethereof, in the form of a water-soluble salt, can be introduced onto thefilter layer. As the water flows through the filter, the activeingredient becomes dissolved therein.

Where it is desired to provide the compounds of Formulas I, 1(a) andI(b) in the form of emulsifiable concentrates, such concentrates can beproduced, for example, by reacting the Formulas I, I(a) or I(b) basewith a quantity of acid, for example, acetic acid, slightly in excess ofthat theoretically required for salt formation and adding such salt towater. In the alternative, an emulsifiable concentrate can be obtainedby treating the Formulas I, I(a) or I(b) compounds with a quantity of asuitable emulsifier which is sufficient to emulsify the compound whenmixed with water.

For a fuller understanding of the nature and objects of this invention,reference may be had to the following examples which are given merely asfurther illustrations of the invention and are not to be construed in alimiting sense.

Example 1 In this example, 500 ml. of concentrated (95100%) acetic acidwas added to, and stirred in, 9.5 liters of Water. Thereafter, 2.5 kg.of N,N'-bis-(1-methyl-3-[2,6,6 trimethylcyclohexyl] -propyl 1,6-hexanediamine was added to the aqueous acetic acid solution. Theproduct, thus obtained, was in the form of a clear concentrate capableof being diluted further with water.

1.0 liter of the concentrate, produced as described in the precedingparagraph, was introduced, with stirring, into a sprinkling can ofliters capacity, following which it was diluted to about 10 liters withwater. This solution was added to a tank containing about 50 cubicmeters of water. Dissolution of the concentrate in the water wasfacilitated by stirring.

It was found that this treatment effectively inhibited the growth ofalgae in the tank for a considerable length of time.

Example 2 A concentrate was produced, in the manner described in Example1 using, with but one exception, the same ingredients and the samequantities thereof as were used in Example 1. In this example, the 2.5kg. of N,N'-bis- (1-rnethyl-3-[2,6,6 trimethylcyclohexyl] propyl) 1,6-hexanediamine used in Example 1 was replaced with 2.5 kg. of a mixturecomprising equal amounts of N,N'-bis- (1,5,9 trimethyldecyl) 2,2dimethyl 4-methyl-1,6- hexanediamine and N,N-bis-(1,5,9 trimethyldecyl)2- methyl-4,4-dimethyl-1,6-hexanediamine.

It was found that when 1.0 liter of the concentrate was diluted to 10liters with water and added to a tank containing about 50 cubic metersof water, the growth of algae therein was inhibited for a significantperiod of time.

Example 3 A concentrate was produced, in the manner described in Example1, using, with but one exception, the same ingredients and the samequantities thereof as were employed in Example 1. In producing theconcentrate of this example, however, there was used 2.5 kg. of amixture of equal quantities ofN,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl] -propyl)2,2-dimethyl-4-methyl-1,6-hexanediamine and N,N'-bis-(1methyl-3-[2,6,6-trimethylcyclohexYlJ-propyl)-2-methyl-4,4-methyl-1,6-hexanediamine in place of the 2.5 kg. ofN,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexylJ-propyl)1,6-hexanediamine employed in Example 1.

It was found that when 1 liter of such concentrate was diluted withabout 10 liters of water and added to a tank containing about 50 cubicmeters of water, the growth of algae therein was effectively inhibitedfor a considerable length of time.

Example 4 In this example, 250 grams of N,N'-bis-(1-methyl-3- [2,6,6trimethylcyclohexyl]-propyl)-1,6-hexanediamine dihydrochloride wasincorporated into a tightly woven cotton sack. This sack was affixed tothe water inlet orifice of a tank. The tap was opened and water wasallowed to flow in a rapid stream through the cloth sack into the tank.The active ingredient was thus carried into the tank, dissolved in thetank water. The tank was then filled to a capacity of 50 cubic meters ofwater.

It was found that the growth of algae in the tank was effectivelyinhibited for a considerable period of time by the treatment describedherein.

Example 5 In this example, 250 grams of N,N-bis-( 1,5 ,9-trimethyldecyl)1,6 hexanediamine dihydrochloride were introduced into a swimming pool,equipped with a rotary pump and filter installation, having thedimensions of 4 meters x 7 meters. The pool was filled with water to thedepth of 1.8 meters. The active ingredient was incorporated into. thesystem by adding it to the circulating water prior to the passage of thewater through the filter. The active ingredient became dissolved in thewater.

It was observed that the growth of algae was effectively inhibited byincorporating the active ingredient in the system in this manner.

Example 6 In this example, there was used a glass aquarium containingabout 10 liters of water. The water in this aquarium, kept in constantmotion by the continuous passage of air, was maintained at a temperaturewithin the range of about 20 to about 25 C. This aquarium was lit with amercury vapor lamp. There was added thereto N,N-bis- (1 methyl3-[2,6,6-trimethylcyclohexyl]-propyl)-1,6- hexanediamine at a level of 2parts per million parts of water.

A second aquarium was set up, identical to that described in thepreceding paragraph, containing the same active ingredient but at alevel of 2.5 parts per million rather than the 2.0 parts per millionmentioned heretofore. Furthermore, nine additional glass aquaria wereset up to evaluate eight other compounds, identified in the table whichfollows, at the concentration indicated therein.

On the next day, the eleven aquaria, together with four aquaria of thesame kind which did not contain an inhibi-tor against algae growth, wereeach innoculated with the same quantity of an algae suspension. After aperiod of about 21 days, the extent of algae growth in each aquarium wasascertained, measured in terms of the of water turbidity. The resultsobtained in these experiments, together with an identification of theactive ingredient and the concentration thereof present, are set forthin the table which follows:

Algal growth Concentration in percent of of compound the water Compoundin ppm. turbidity Control (without protectant) 0 60 Do 0 70 Do 0 70 Do 060 (1)N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]-propyl)-1,6-hexanediamine.2. 0 0-1 2. 5 0 (2) N,N-bis-(1,5,9trimethy1decyD- 2. 0 021,6-hexanediamine. 2. 5 0 (3) N,N-bis-(1,5,9-trimethyldeeyD-1,2-ethy1enediamine 2. 0 0-20 (4) N,N-bis-(1,5,9-trirnethyldecyl)-N,N-dimethyl-1.2-ethylendiamine. 2. 5 0-20 (5)N,N-bis-(1,5,9-trimethyldecyl)- N,N-dimethy1-l,6-hexanediamine- 2 0 020(6) N,Nbis-(l-methyl-3-[2.6.6-trimethylcyclohexyl]-propy1)-N,N-dirnethyl-l,4-butane-diamine bis- (methoehloride) 2. 5 020 (7) N ,N-bis-{1-methy1-3-[2,6,6-trirnethylcyclohexen-(1)-yl]-propyl}-N,N-dimethy1-1,6-hexauediamine bis-(methobromide) 2. 5 0-10 (8)N,N'biS-(1-methyl-3[2,6,6-trimethylcyclohexyl1-propyl)-1,2-ethanediamine 2. 5 0-10 (9)N,N-bis(1-methyl-3-[2,6,6-trimethylcyclohexyH-propyl)-N.N-dimethyl-Lfi-hexanediamine 2. 0 [H0 The foregoing results demonstratethat the compounds tested are highly effective in controlling the growthof algae.

We claim:

1. Process for the control of algae growth in an aqueous system whichcomprises adding to said aqueous system an effective amount of at leastone compound selected from the group consisting of (1)N,N'-bis-(1,5,9-trimethyldecyl) 1,6 hexanediamine,N,N-bis-(1,5,9-trimethyldecyl) 1,2 ethylenediamine,N,N'-bis-(1,5,9-trimethyldecyl)-N,N'-dimethyl 1,2 ethylenediamine,N,N-bis- (1,5,9 trimethyldecyl) N,N dimethyl-1,6-hexanediamine, N,N' bis(1 methyl 3-[2,6,6-trimethylcyclm hexyl] propyl) 1,6 hexanediamine,N,N'-bis-(1-methyl 3 [2,6,6-trimethy1cyclohexyl]-propyl)-N,N-dimeth yl1,4 butanediamine bis-(methochloride), N,N'-bis-{1 methyl 3 [2,6,6trimethylcyclohexen-(1)-yl]-propyl}- N,N dimethyl 1,6-hexanediaminebis-(methobromide), N,N' bis (1 methyl 3 [2,6,6-trimethylcyclohexy1]-propyl) 1,2 ethanediamine and N,N'-bis-(1-methyl-3- [2,6,6trimethylcyclohexyl] propyl) N,N-dimethyl- 1,6-hexanediamine; (2) acidaddition salts thereof; and (3) a quaternary derived therefrom.

2. The process of claim 1 whereinN,N'-bis-(1,5,9-trimethyldecyl)-1,6-hexanediamine is used as the algaecontrolling compound.

3. The process of claim 1 whereinN,N'bis-(1,5,9-trimethyldecyl)-1,2-ethylenediami11e is used as the algaecontrolling compound.

4. The process of claim 1 wherein N,N'-bis-(l,5,9-trimethyldecyl)N,N'-dimethyl-1,6-hexanediamine is used used as the algae controllingcompound.

5. The process of claim 1 wherein N,N-bis-(1,5,9-trimethyldecyl)N,N'-dimethyl-1,6-hexanedimaine is used as the algae controllingcompound.

6. The process of claim 1 wherein N,N-bis-(1-methyl- 3 [2,6,6trimethylcyclohexyl] propyl)-1,6-hexanediamine is used as the algaecontrolling compound.

7. The process of claim 1 wherein N,N-bis-(l-methyl- 3 [2,6,6trimethylcyclohexyl]-propyl)-N,N-dimethyl- 1,4 butanediaminebis-(methochloride) is used as the algae controlling compound.

8. The process of claim 1 wherein N,N'-bis{1-methyl-3- [2,6,6trimethylcyclohexen (1) y1]-propy1}-N,N-dimethyl-1,6-hexanediaminebis-(methobromide) is used as the algae controlling compound.

9. The process of claim 1 wherein N,N-bis-(1-methy1- 3[2,6,6-trimethylcyclohexyl]-pro1py1) -1,2-ethanediamine is used as thealgae controlling compound.

10. The process of claim 1 wherein N,N-bis-(1-methyl- 3-[2,6,6-trimethylcyclohexyl] -propyl) -N,N-dimethyl-1,6- hexanediamine isused as the algae controlling compound.

References Cited UNITED STATES PATENTS 3,064,039 11/1962 Goldberg260-501 3,064,052 11/ 1962 Goldberg 260563 ALBERT T. MEYERS, PrimaryExaminer D. M. STEPHENS, Assistant Examiner U.S. Cl. X.R. 424325

